Fibroin spinning solutions



Reiauea May 21, 1940 Re, ,4561

UNITED STATES PATENT OFFICE FIBROIN SPINNING SOLUTIONS Rudolph S. Bley, Milligan College, Tenn., assignor to North American Rayon Corporation, New York, N. Y., a corporation of Delaware No Drawing. Original No. 2,145,857, dated February '7, 1939, Serial No. 203,444, April 21, 1938, which is a division of application Serial No. 59,912, January 20, 1936. Application for reissue March 16, 1939, Serial No. 262,236

16 Claims. (Cl. 10638) droxides may be used for this purpose, such as triethyl-benzyl-ammonium hydroxide, dimethylphenyl-benzyl-ammonium hydroxide, diethylphenyl-benzyl-ammonium hydroxide, dibutyl- The present invention relates to a process of manufacturing solutions of proteins, such as fibroin casein, gelatin, wool and alginic acid, from which the proteins may be precipitated by suitable magenta phenyl-benzyl-ammonium hydroxide, dimethyl- One object of this invention is to prepare a spintolyl'benzyl'ammomflm cumethyl' ning solution containing a protein selected from amyl'benzyl'ammomum hydroxlde' dlmethyl' the group consisting of silk fibroin, wool, gelatin, dlbenzyl-ammonium hydroxide, benzyl-Pyrialginic acid and casein from which artificial proddonium hydroxide, dibutyl'dibenzyl'ammomum ucts, such as filaments, yarns, ribbons, films, etc., hydroxide, tolyl'pyridonium hydroxide, In

my be formed, other words, I may use any water-soluble, high- Another object of my invention has to do with molecular quaternary ammonium yd xide the preparation of a spinning solution by dissolvwhich has a strong basic reaction and which is ing fibroin in a quaternary benzyl substituted amable to dissolve fibroin, W001, 0811111056, Benzyl ju base. substituted ammonium hydroxides are able to A third object of my inventio r l t to th dissolve such substances in relatively short periods mgnufagture of fibroin spinning 1 11 by 11 of time. to form clear, filtrable solutions. The solving a fibroin, such as natural silk, in a quaterfibroin can be precipitatedfrom Such solutions y nary benzyl substituted ammonium hydroxide. diluting them w Water or y Causing the A fourth object of thisinvention has to do it monium base to react with acids, acid salts and the preparation of a spinning solution containing e like. However. it is to be noted t -q eens cellulose or cellulose derivatives and fibroin, from solutions of benzyl substituted ammonium hywhich these substances may be precipitated in droxides should be preferably of about to 50% hydrated form. strength, i. e., about 2 normal. It is also prefer- 25. Other objects of my invention will become apable to dissolve fibroin in quaternary ammonium parent to those skilled in the art from a study bases at an elevated temperature for the formaof the following specification. tion of clear filtrable solutions. However, care I am well aware that processes are already must be exercised to avoid decomposition by the known for dissolving silk fibroin in ammoniacal solvent by raising the temperature too high. Al-

copper hydroxide, etc., to produce spinning soluthough it has been found that such fibroin solutions therefrom. However, such solutions have tions keep well on standing at ordinary room proven unstable due to degradation of the fibroin temperature, the degradation of fibroin may be molecule, this degradation resulting in a decrease practically overcome by storing said solutions at in viscosityof such fibro n solutions. Inaccorda low temperature. The solutions may be diluted 3!! ance with the prese invention t is degradation to some extent with water without causing preof the fibroin moleculeis substantially countercipitation f fibroin provided suitable emulsifying acted by dissolving natural silk in solutions of agents, such as trimethyl-benz'yl-ammonium quat rna y yl substituted ammonium bases oleate, alkali metal salts of fatty acids, etc., are

I have found y experimfintatimfl that fibroin added thereto in suitable proportions.

40 be rap y and 00111111915943 dlssolved hlgh" Any known type of delustering agent which is molecu Organic ammomum bases havmg the stable in quaternary ammonium bases, such as genera-1 structure oils, pigments, dyestufi's, etc., may be dispersed 0.115013, l by suitable means in these fibroin solutions for a the production of soft-lustre or colored products therefrom.

8 I Instead of using a fibroin solution per se for in which R2 and reprwent y m the production of filaments, yarns, films, etc., I and/o1 amlkyl groups or substituted denvatwes ma form mixed spinning solutions containing thereof. In addition, I have found that benzy y n b h b t d uatemary ammonium hydroxides for example fibroin and ce ulose, since at su substlm e q mt m f r dissolving, fibroin W001 stances may be dISSOlVBd 1n quaternary amare espercmuy in in s lutions Althou h mmium hydroxides" FM this I may $3133 8 sflnmefhyhbenzyLammonium dissolve for example natural silk and cellulose droxlde is an excellent, solvent for fibroin, wool, or a cellulose derivative, such as cellulose esters etc., other quaternary benzyl-ammonium hyand ethers in a concentrated, aqueous solution of a benzyl substituted ammonium hydroxide such as trimethyl-benzyl ammonium hydroxide, etc. The fibroin-cellulose or fibroin-cellulose derivative solution may be subsequently spun into water, 5 dilute acids or salt solutions to form filaments, yarns, ribbons or films. Solutions may also be spun containing fibroin, cellulose and a rubber latex. The solutions, set forth above, may be spun in funnels like cuprammonium cellulose or they may be precipitated and coagulated like viscose in setting baths. The ooagulated products may be collected on spools orin centrifugal pots. Cellulose sponges may be formed in molds in wellknown manner. Any known delustering agent which is stable in quaternary benzyl substituted ammonium bases may be added in suitable 'amounts to fibroin, fibroin-cellulose, fibroin-cellulose derivative or fibroin-wool or mixtures thereof to modify the lustre and other physical characteristics of the finished products. The ammonium bases may be recovered from the setting baths by suitable means and re-employed for the dissolution of fibroin, cellulose, wool, etc., to render the process more economical.

Example 1 Natural silk, i. e., fibroin, is dissolved at a moderate temperature in a to 50% solution of trimethyl-benzyl ammonium hydroxide until a solution of sufiicient viscosity 'is obtained. The spinning solution, thus prepared, is spun with the assistance of spinnerettes into an acid setting bath containing for example dilute sulphuric acid and sodium sulphate. The threads are collected on spools or in pots, 'washed and dried. Wool, gelatin, alginic acid or casein may be dissolved in similar manner to form solutions which are spun like silk fibroin.

Example II Fibroin, wool, gelatin, alginic acid or casein solutions with or without cellulose additions are diluted with water after the addition of a suitable emulsifying agent, such as trimethyl-benzyl oleate to such extent that the solid phase is not precipitated, spun and after-treated in accordance with the methods set forth above.

Instead of feeding the spinning solutions, set forth above, singly to the spinning nozzles, I may extrude for example a fibroin solution together with a cellulose solution from a single or a plurality of spinnerettes and obtain composite products consisting of natural silk and cellulose filaments, etc. In this manner, I may 70 also produce mixed products consisting of natural silk, wool and cellulose, etc. Furthermore, I may admix pigments or other solid and liquid delustrants with my spinning solutions for the production of yarns composed of differently colored filaments. etc. In other words, according to the present invention, any method known in the rayon art may be used to modify the physical properties of products manufactured from my novel spinning solutions. Instead of completely dissolvingthe carbohydrates in benzyl-substituted quaternary ammonium hydroxide, they may be pretreated therewith and subsequently xanthated with carbon bisulphide to form solutions from which artificial silk may be spun. I wish to emphasize that the substances, set forth aboya. may be truly dissolved in the quaternary ammonium hydroxides or merely finely dispersed therein.

Modifications of my invention will readily be recognized. by those skilled in the art, and I desire to include all such modifications coming within the scope of the appended claims.

I claim:

l. A spinning solution for the manufacture of artificial products comprising a protein selected from the group consisting of silk fibroin, wool,

gelatin, alginic acid and casein finely dispersed in a quaternary tolyl substituted ammonium base having the structure I in which R1, and R2 represent a radical selected from the group consisting of alkyl radicals, aryl radicals, aralkyl radicals, substituted alkyl radicals, substituted aryl radicals and substituted aralkyl radicals, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

3. A spinning solution for the manufacture-of artificial products comprising a casein finely dispersed in a quaternary tolyl substituted ammonium base having the structure a temperature not exceeding. ordinary room temperatures.

4. A spinning solution for the manufacture of artificial products comprising an alginic acid finely dispersed in a quaternary ammonium base having the structure in which R1 and R2 represent a radical selected from the group consisting of alkyl radicals, aryl radicals, aralkyl radicals, substituted alkyl radicals, substituted aryl radicals and substituted aralkyl radicals, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

5. A spinning solution for the manufacture of artificial products comprising a protein selected from the group consisting of silk fibroin, wool, gelatin, alginic acid and casein finely dispersed in a dimethyl-tolyl-benzyl-a.mmonium hydroxide, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

6. A spinning solution for the manufacture of artificial products comprising a silk fibroin finely dispersed in a dimethyl-tolyl-benzyl-ammonium hydroxide, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

'7. A spinning solution for the manufacture of artificial products comprising a casein finely dispersed in a dimethyl-tolyl-benzyl-ammonium hydroxide, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

8. A spinning solution for the manufacture of artificial products comprising an alginic acid finely dispersed in a.dimethyl-tolyl-benzyl-ammonium hydroxide, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at in which R1 and R2 represent a radical selected from the group consisting of alkyl radicals, aryl radicals, aralkyl radicals, substituted alkyl radicals, substituted aryl radicals and substituted aralkyl radicals together with a cellulosic substance selected from the group consisting of cellulose, cellulose esters and ethers, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

10. A spinning solution for the manufacture of artificial products comprising a silk fibroin finely dispersed in a quaternary tolyl substituted am monium base having the structure in which R1 and R2 represent a radical selected from the group consisting of alkyl radicals, aryl radicals, aralkyl radicals, substituted alkyl radicals, substituted aryl radicals and substituted aralkyl radicals together with a cellulosic substance selected from the group consisting of cellulose, cellulose esters and cellulose ethers, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding room temperatures.

11. A spinning solution for the manufacture of artificial products comprising a casein finely dispersed in a quaternary tolyl substituted ammonium base having the structure CHE-00H! 010E50 in which R1 and R2 represent a radical selected from the group consisting of alkyl radicals, aryl radicals, aralkyl radicals, substituted alkyl radicals, substituted aryl radicals and substituted aralkyl radicals together with a cellulosic substance selected from the group consisting of cellulose, cellulose esters and ethers, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

12. A spinning solution for the manufacture of artificial products comprising an alginic acid dispersed in a quaternary tolyl substituted ammonium base having the structure N-R1. HO/ RI in which R1 and R2 represent a radical selected from the group consisting of alkyl radicals, aryl radicals, aralkyl radicals, substituted alkyl radicals, substituted aryl radicals and substituted aralkyl radicals together with a cellulosic substance selected from the group consisting of cellulose, cellulose esters and cellulose ethers, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

13. A spinning solution for the manufacture of artificial products comprising a protein selected from the group consisting of silk fibroin, wool,

gelatin, alginic acid and casein finely dispersed in a dimethyl-tolyl-benzyl-ammonium hydroxide together with a cellulosic substance selected from the group consisting of cellulose, cellulose esters and cellulose ethers, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

14. A spinning solution for the manufacture of artificial products comprising a silk fibroin finely dispersed in a diamethyl-tolyl-benzyl-ammonium hydroxide together with a cellulosic substance selected from the group consisting of cellulose, cellulose esters and cellulose ethers, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

15. A spinning solution for the manufacture of artificial products comprising a casein finely dispersed in a dimethyl-tolyl-benzyl-ammonium hydroxide together with a cellulosic substance selected from the group consisting of cellulose, cellulose esters and cellulose ethers, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding ordinary room temperatures.

16. A spinning solution for the manufacture of artificial products comprising an alginic acid finely dispersed in a dimethyl-tolyl-benzyl-ammonium hydroxide together with a cellulosic sub stance selected from the group consisting of cellulose, cellulose esters and cellulose ethers, said solution having the property of substantially retaining its viscosity on standing for relatively long periods of time at a temperature not exceeding, ordinary room temperatures.

RUDOLPH S. BLEY. 

